Process of making halogenated products



'ramas may as, reza UNET@ ATS 'AN BYRON E. ELDRED, F NEW YORK, N. Y., ASSIGNOR, IBY MESNE .B SSlGNMENTS, TO CARBIDE AND CARBON CHEMICALS CORPORATION, .A CORPORATION OF NEW YORK.

rasee PROCESS OF MAKING HLOGENATED PRODUCTS.

Application filed February 8, 1917. Serial No. 147,461.

To all whom z't may' concern? Be it 'known' that I, BYRON E. ELDRED, a citizen of the United States, residing at New York, in the county of Queens and State of New York, have invented certain new and useful lmprovements in Processes of Making Halogenated Products, of which the following is a' specification.

This invention relates to processes of making halogenated products; and-it comprises a method of vreacting upon unsaturated gaseous hydrocarbons with chlorin in the presence of steam to produce the bodies known' as chlorhydrins, wherein a continuous current of gases, vapors and steam is established and maintained in and through one or more `vertical reaction chambers, passing therefrom to condensing means, such current being formed initially of steam, oil gas'and chlorin and receiving at intervals during its passage successive further ad ditions of chlorin and of oil gas, whereby the same steam serves as a diluentmeans in a successive series of reactions between chlorin and oil gas; all as more fully hereinafter set forth and as claimed.

In breaking up petroleum oils, such as solar oil, gas oil, petroleum resid'uum, Wax;` tailings, kerosene, crude oil, etc. by heat, an oil gas may be obtained which is relatively rich in unsaturated compounds; frequently going as high as 5() per cent of total unsaturated gaseous hydrocarbons (bromin absorption). For the most part these unsaturated gases are olefins, being mainly ethylene and propylene with small amounts of the butylenes. Good gas for the present purposes may be made by passing such an oil through a retort heated to 700O C. or thereabouts. Higher or lower temperatures may be employed; this depending somewhat on the apparatus, the rate of oil feed, ete. Operation may be under extra pressure or under reduced pressure. Ordinary atmospheric pressure works well. It is desirable to pass the oil through the gasif ing zone at a rate rather more rapid than t e rate of gasification, i. e. so that more orless ungasified oil passes through; and then quickly cool the lssuing gas. The excess of oil condenses and separates as a fog of fine suspended droplets and serves as an effective scrubbing means for removing non-gaseous volatile hydrocarbons, such as gasoline, etc. Further purification, such as treatment with oXid of iron, etc., maybe resorted to removin sulfur and other impurities. The olefins o oil gas readily enter into reaction with chlorin, and with proper regulation. of conditions the reaction is not explosive or destructive. The products which are formed depend however upon the conditions. Taking ethylene as typical, one product which may be formed is what is known as ethylene dichlorid or Dutch liquid, C2H4Cl2. Propylene and the butylenes form similar materials which may also here be called, for the sake of a l name, Dutch liquid. In practice, some moisture or other catalyst appears to 'be necessary for producing the reactions which lead to the production of Dutch liquid; and particularly with ethylene. The olefin dichlo- .rids, or Dutch liquids are heavy oily bodies Ethylene chlorhydrin for example is C2H4OHC1. It willl be observed that it differs from ethylene chlorid not only in containing less chlorin but also in, that it contains .OIL derived from the water present and taking part in the reaction. Attendant upon the chlorhydrin forming reaction is the production of HCl or hydrochoric acid. Half the chlorin used reappears' as chlorhydrin and half as HC1. In practice inthe operation of making chlorhydrin, utilizing the described reaction it is found that as HC1 accumulates in the zone of reaction the tendency towards the production of chlorhydrins' lessens 4while the tendency to the production of the olefin chlorids increases. This is undesirable for the reason that although the olefin chlorids are technically valuable materials yet they are not as desirable as the chlorhydrins. Tfhe chlorhydrins are not only valuable as solvents for resins and other coatingA materials but have the further value of being materials from which a wide variety of other useful prodlinteraction* of chlorin, oil gas'an' is found that a relatively large amount of.

ucts may be readily made,.as 4for instancev`l glycols, acetates, formates, butyrates, benzo ates,`etc. The possibilityof an economical productionof glycols, which may be utilized -forthe purposes for which glycerinv is now used, renders the manufacture ofl chlorhydrin particularly importanti The chlorhydrins of oil `gas allhave nearly the saine boiling point and the mixture produced in the present process,y for technical purposes, is practically a unitary substance. In a dry condition they boil between 125-135 (1, while in the presencev of' water their boilmg ,point is several degrees below 100 C. Thislatter fact is utilized in the present inven- In the manufacture of chlorliydrins by steam, it

steam is necessary tofdilute the gas and chlorin'and insure a 'good' production of 'chlorhydrins and a corresponding restriction of .the production of Dutch liquid" In the present invention 'I have devisedv a .method of performing the ,statedreaction wherein substantially the same steam is used which now contains chlorhydrins, I add a further portion of chlorin and one of oil gas. They may' be added together but I ind it better to add them in succession, first the chlorin and then the oil gas. I may continue this portionwise addition of reactive gas and reactive chlorin, with a pause between each addition or, which is the same thing, with' a flowing'current making the additions at spaced`points along the path of the current, untilV the proportion of chlorhydrin vapors to the s'team is a maximum which may be determined by tests of samples. When once determined for a given size of apparatus, the plant may thereafter be run in the same general way. At this time I pass the current of mixed vapors through a condenser to condense and recover the vapors. In practice I find that with an apparatus of convenient size an addition of four or five successive portions of gas and of chlorin to the same gas-vapor mass may be made, although it is within the limits of the present invention to use a greater or less. number of successive additions. I regardthis invention as covering any process wherein oil gas, steam and chlorin are allowed to react and prior to lsage through theapparatus.

vLacasse gas is produced in the same mass or body; 1'

that is in the'pr'esence of the same steam whichserved for dilution and reaction'with the first vaddition of gas and chlorin. By

cutting'down the amount of steam I can in 'crease the amount of Dutch liquid formed.

Or by runningthe whole apparatus rather densed steam/formed, which increases the 475 hotter and diminishing the amount' of conamount of HC1 in the vapor form, I can` I also increase the `production of Dutch liquid.

The proportion of chlorhydrin and'of Dutch liquid which yI may wish to yproduce depends upon economic conditions. JBoth are valuable solvents and of economic value. I ordinarilyA` desire to increase the 'chlorhydrin atthe expense ofthe Dutch liquid for the reasonsstated ante.`

In the stated reaction as already noted, the presence 'of HCl in the zone olf.' reaction But i is' undesirable and since itforms inA the reaction itself, means must be provided for removing it. Such means may be water co`n. densed from "the steam added and in this event I may desire' to add small 'further replenishing additionsof steam tothe current of reacting gases and vapors in their pas;v

Such addi" tions of steam are convenient in any event, 'and particularly in introducing'the'chlorin; not only because the chlorin must be diluted with the steam butl because, using'the steam as an injecting means, it allows using chlorin in Ithe chlorin line under less than atmospheiic pressure by reason of the sucking actionvof thejinjector. This is particularly convenient in using chlorin directly from electrolytic cells, such cells being ordinarily run under suction 'to avoid nuisance.' Usually the cells are run hot, say at about 80 C.,- and where hot moist chlorin can be taken directly from the cell and used as economizing both heat and steam. The' cells may with advantage be run hotter than is the usual practice, even up to 100 C. since this lessens their resistance while the more water vapor comes forward with the chlorin the betterfor the present purposes.

vin the present invention it is advantageous The HCl ,which forms inthe vapor cur- 1 rent as a result of the cillorhydrin reaction may be removed in other ways than by simple washing out with condensed water. One such yway which has proved convenient in practice is described and claimed 'in a copending application of one J. M. Moness and. broadlystated, consists in *maintaining l in the sphere of reaction solid manganese dioxid or other material capable of reacting.

withHCl to oxidize such HCl and liberate chlorin. In so vdoing not only is the HC1 removedbut half its chlorin `is regained for naaeeo use in the reaction. As already noted, in the production of chlorhydrins from oil gas and steam only half the chlorin reappears in the chlorhydrin, the other half forming HC1. By the use of Mn()2 half of this HC1 is regained as chlorin. This expedient may be advantageously used in connection with the process of the present invention; but is not .necessarily so used. Vhen used, I customarily pass the reaction mixture after each successive addition of.chlorin and of gas into contact with granular manganese dioxid. Instead of using the granular manganese dioxid, a suspension-of` WVeldon mud or the like may be employed with suitable apparatus permitting transmission of such suspension through the same as a countercurrent. The reaction of the HCl on the manganese dioxid forms manganese chlorid which dissolves in the water condensing from the steam and drains away. Advantageously I intercept the manganese chlorid solution formed in later stages in the course of the path of the mixed gas and vapor current and remove it without forcing it to pass in a countercurrent against the whole current of gases and vapors. Where using granular manganese dioxid it has another function thanv the chemical one just stated in that` it acts as a scrubbing and mixing means. The gases and vapors forced to pass between the granules are effectively mixed and the layers of liquid on thesurface of the ranules give a good scrubbing action. ther granular materials which are chemically inert may be used in lieu of the manganese dioxid granules in securing this scrubbing result.

In the accompanying illustration I have shown more or less diagrammatically, partly in vertical section and partly in elevation, an apparatus adapted for use in the operation of the described process.

In this showing,1is a pipe leading from a suitable source (not shown) of oil or the like to be gasified. The oil is fed int-o retort `Zwhich is kept ata suitable temperature by oil burner 3 in furnace chamber 4f. Any unvaporized oil passing through the retort may be led away by drip 5 and collected for return. The gas produced in the operation passes through 6 into cooling land quieting chamber 7; In practice it is best to run the gas making operation so that a considerable amount of unchanged oil vapors remain in the issuing gas. 0n cooling in this chamber the oil condenses and forms a fog which serves as an efficient scrubbing means for removing any gasoline, etc. which may be in the gas. To assist in quick cooling this quieting chamber may be provided ras shown. with cooling coil 7a. Oil condensing is withdrawn by drip 7". Cooled and settled gas passes from this tank through pipe 8 provided with a number of of lvalved branches allowing communication with a reaction chamber or chambers at a` As shown, the reactlon plurality of points.

chamber is made intwo sections or subvinto the reaction aparatus at a plurality of successive points. s shown, chlorin may be blown into the apparatus at each of these points through a steam injector 12. Spanning the reaction chamber at various points along its length are perforated cross plates 13 which serve in securing thorough admixture, unobstructed mixing chambers occurring between each alternate pair of these cross plates 13. The alternating sub-chambers may here be called oxidizing chambers. Mounted on alternate plates are further mixing devices 15 which as shown are two sets of simple annuli mounted out of alignment. Upon the top annuli rests a layer, 16, as shown, of granulated manganese dioxid or other granular material which may or may not have a chemical function. Between these sections, which may be called oxidizing sub-chambers, are the unobstructed sub-chambers 17. As shown, the portion of.

the reaction chamber or sub-tower through which the current of gases and vapors first passes is closed off at the top by dome 18 through which passes a conduit 19 leading the gases and vapors to the base of the companion and continuing reaction chamber or sub-tower. The first sub-tower may be designated as a whole by 20 and the second as 20. 20 is exactly like the first sub-tower. The unobstructed chamber at its base is designated as 21. At the top of the tower is an unobstructed chamber 22 with which communicates a sort of reflux arrangement 23 provided with perforated cross shelves 24. This serves to condense and return a portion of the excess of steam going over.r

The-somewhat cooled gases and vapors pass through 25 to condenser 26 in tub 27. Uncondensed gases and condensed liquids pass on into receiver 28 from which gases may beI led to exit through 29 while condensed liquid is withdrawn at 30. Steam for the sys.

tem is provided from main 31 havinga number of branches at Variousv points 32. Condensed water holding in solution manganese chlorid, if the layers of manganese Adioxid mentionedv are used, but otherwise `holding in solution HC1, maybe withdrawn through traps 33. Two of these traps are yshown allowing each of the sub-towers t be `drained separately. Where manganese di- :oxid is employed the layers in the reaction #chamber may be replenished from time toy timevthrough hand holes 34. The sub-towl connected by flanged unions 35 in which mayw,

ers maybe made' of a plurality of sections be placed any suitable lute. As shown, the condensate in this receiver is condensed into two layers,a `lower layer A and an upper layer B.

ln the operation of the above apparatus. the gas which is made in 2 (there may be a number of these retorts operating in parallel) .is taken through 6 and cooled yand freedV ofoil vapors in 7 A portion of the i gas is ledby a branch of pipe Srinto the lowermost unobstructed sub-chamber, or thel first invorder, 9.' Here the gas meets wlth. chlorin from abranch of pipe 11 and steam.

froml. As shown, steam and chlorin are The introducedat alower level than gas.

msteam,g.gasand chlorin are thoroughly in- ...fterr'nfixedand reaction begins. @Admixture and reaction are. perfected by passagev of,

thecurrent through the perforations of 13, the staggered annuli 15- and the granular l-layer. As thc-reaction with the production'. of chlorhydrin,y progresses, HC1 is.for'med.il

Where layers 16 of manganese dioxid are employed, this HC1 is there oxidized and converted into water and free chlorin, this -free chlorin in its turn reacting with the olefins. l The manganese chlorid dissolves in condensing water and is drained away through 33. Where another granular material is substituted for the manganese l mixing and scrubbing means. As the chlo--` dioxid the HC1 produced is dissolved or taken up by condensing water and escapes as an acid solution in the same way. Where manganese dioxid. is'not employed, layer 16 may consist of broken glass, broken stoneware, quartzfragments, etc. serving as a rin and olefins react they tend to disappear and are replaced by vapors of chlorhydrins; lthe whole apparatus being at a temperature ("-100o C.) such that the chlorhydrins remain in the vapor form in the presence ot the steam. The desired temtion of chlorin is added from a branch of pipe 11 and another port-ion of gas from a branch of pipe 8. More or less steam may be added also at this point by the `steam inl jector shown. The gas current which now Lacasse ldownward and escapes at the same trap 33.

The gases and vapors are now led through cross-over 19 into another unobstructed chamber 21 where ,a further portion of chlorin is added. from another branch of pipe v11. If desired further steam may be added through 32 to maintain the heat and dilution in the passagethrough the cross-over. More chlorin is nowintroduced with a little steam from.a.branchof pipe 31. IGras is `introduced `from 4a ,branch of pipe 8.: The

chlorin and gas so. introduced are mixed lwith the vapors inpassing through the perforated cross plate and the ystaggered annuli, and passing. thence Ythrough fragmentary material 16.,L vA further vportion of chlorhydrins is roduced, Thegases and vapors now pass t rough-another perforated cross plate into therunobstructed space 17 where more chlorin and gas,..and if desired more steam, .are introduced.- lThe ymixture now passes througha cross plate, staggered annuli and fra rmentary material asbeore. If desired a little more. steam may be added through` pipe 32. The HC1 solution or manganese chlorid solution, as the case maybe,

rains through the whole chamber 20 to trap 33. The mixture of gases and vapors passes upward through 24 and is artially re'luxed and fractionated with the aidof cross plates 23. Condensed liquid drains back into the sub-tower 20'. Alow boiling mixture of vapor passes through 25 to the condenser 26. In 28 the two layers shown, A and B, may be of condensed Dutch liquid and watery solution of'chlorhydrins or A may be av layer of condensed chlorhydrins and B a saturated solution of the same.

As will be evident, the presentI invention comprises establishing andmaintaining a body or mass of steam (which in practice is a flowing mass or current) and adding chlorn'and gas to the body portionwise, time bein allowed for reaction between additions. n so doing, the amount ('or concentration) of gas and of chlorin in the mass is not great at any one time while in the aggregate considerable amounts ofv both are used in connection with a relatively small amount of steam. The advantage of this in economizing heat and space is obvious.

Y The granular fragmentary mass or layer 16 shown has as stated a mechanical function as promoting admixture of the gases and vapors; and-this function is an important one. Good and uniform admixture of materials varying as Widely in specific grav- :casacca ity as chlorin, oil gas, steam and chlorhydrin is diilicult to secure. lf the granules are M1102 they su eradd a chemical function in removing Cl and converting it into C12; if they are pottery fragments, broken stone, etc., they have what may be called 4a physical function in removing HCl since their surfaces are covered with a flowing film of hot condensed moisture which takes up HG1 without absorbing chlorhydrin. In either event it is advantageous to remove the condensate .(which is a solution of MnCl2 or HC1 as the casema-y be) at a plurality of points along the course of the advancing vapor current to prevent too great concentration. 'lwo points ot removal (elements 33) are shown, but more may be provided. f

While l regard the particular internal structure of the reaction chamber shown as advantageous for the present pur oses, I may of course use other types o tower or reaction chamber provided they are equipped to accomplish my object of adding gas and chlorin in successive small portions to an advancing current of gases and vapors.

In this specification l have more particularly described my process as applied to oil gas made in the manner described; but it may of course be applied to any good oil gas made in other ways; or to any similar gas rich in olefins such as the gas trom cracking stills -used on petroleum; gases from coal or shale distilled at low temper-4 atures, etc. And as these gases are mainly used as convenient sources of the gaseous olelins, ethylene, propylene and the butylenes, it is obvious that these olelins themselves made in any convenient or suitable manner may be employed in the present process, singly or admixed, without departing from my invention. Ethylene may, for example, be made by partially hydrogenating acetylene with the aid of catalysts, by breaking up alcohol, by fractional separation of liquefied oil gas, etc.

ln a modification of my invention using the manganeseidioxid, instead of blowi'n in chlorin with a current of steam, vapors t? hydrochloric acid and water are blown in to react upon the manganese dioxid' and form chlorin.

In stating the oxidizing function of the manganese dioxid, or the Weldon mud, in the oxidizing chamber, l do not wish to be limited to the theory that the oxidation is entirely conlined to the hydrochloric acid since it ma extend also to the olefins. Such an oxidation would. he attended with neutralization of 'll-ICI.. The manganese dioxid in addition to its oxidizing -uncton also has a neutralizing function. @ther basic oxids which have no particular oxidizing function in ,this relation may be substituted for the manganese dioxid, as for instance zinc oxid, magnesia, etc. For, example, a suspension of magnesia or zinc oxid may be passed through the apparatus to enutralize the hydrochloric acid. rl`he use of carbonates, such as calcium carbonate, etc. is less advisable for the reason that they dilute the gases with CO2.

What I claim is 1. The process of making chlorhydrins from the gaseous olefins which comprises establishing a flowing current of steam and adding to such current successive portions of chlorin and of gas comprising oleins, time for reactions to take place in such current bein a'orded between additions.

2.?llhe process 'of making chlorhydrins from the gaseous olefins which comprises adding chlorin and oil. gas to a body 0f steam and after a time to allow reactions to takeA place adding a further portion of chlorin and a further portion of oil gas to the :body of steam and vapors.

3. The process of making chlorhydrins from the gaseous olefins which comprises establishing a flowing current of steam in a chamber provided with means for absorbing HC1 from such current, and adding chlorin and oil gas thereto as successive small portions.

d. rl`he process of makin chlorhydrins from the gaseous olelins w ich comprises establishing a flowing current of steam in a chamber provided with means for absorb` ing HC1 from such current, and adding chlorin and oil gas thereto in alternating portions, there being a plurality of additions of each along the path of such dowing current.

5. The process of making chlorhydrins -from the gaseous olefins which comprises establishing` `a flowing current of steam through a reaction chamber provided with a plurality' of spaced layers of granular material and admiring with such current lll() prior to its entrance into each of said layers a portion ot chlorin and a portion of oil gas.

6. The 4process orf making chlorhydrins from the gaseous oleins which comprises establishing a flowing current of steam through a reaction chamber provided with a' plurality of spaced layers of granular manganese oxid and admixing with such current prior to its entrance into each. of said la ers a portion or" chlorin and a portion o oil'gas..

7. The process of making chlorhydrins from oil gas olefins which comprises estab'- lishing a lowing current of steam through a reaction chamher provided with a plurality of spaced layers of granular manganese oxid and admiring with such current prior to its entrance into each of said layers a portion of chlorin and a portion of oil gas,

condensed liquid being\drained od such layers and removed from contact with said current at a plurality of points along the path of the current 8. Process for the production of chlorine containing bodies which comprises adding `to a stream of steam, chlorine and oil gas inv a plurality of steps, removing and oxidizing the HC1 formed from the zones of reaction and condensing the steam to recover chlorinated bodies.

9. A process for the preparation of halogen hydrins in which the halogen hydrin is caused to accumulate in an aqueous medium owing to the co-ntinued interaction of a hypohalogenous acid and an olefinic hydrocarbon.

10. A. processfor the preparation of halogen hydrinsin which the halogen hydrin is caused to accumulate in an aqueous medium owing to the continued interaction of a hypohalogenous acid and an unsaturated hydrocarbon of the ethylene series. l

11. A process for the preparation of halogen hydrins in which the halogen hydrin is caused to accumulate in an aqueous medium owing to the continued interaction of a hypohalogenous acid alid ethylene.

12. A process for the preparation of chlorhydrins in which the chlorhydrin is caused to accumulate in an aqueous medium owing to the continued interaction of a hypochlorous acid and an olefinic body.

13. A process for the preparation of chlorhydrins in which the chlorhydrin is caused to accumulate in an aqueous medium owing to the continuedinteraction of a hypochlorous acid and ethylene.

llt-Process for the manufacture of halogen hydrins in which the halogen hydrin is accumulated within an aqueous medium by alternately generating hypohalogenous acidv l within said medium and introducing an oleliniebody into said medium. A 15. Process for the manufacture of halogen hydrins in which the halogen hydrin is accumulated within an aqueous medium by alternately generating hypohalogenous acid within said medium and introducing an oleinic body in a gaseous form.

16. Process for the-manufacture of halogen hydrins in which the 4halogen hydrin isV Lacasse 18. ln theprocess of preparing halogen hydrins byaccumulation thereof within an aqueous medium by continued interaction 'of chlorhydrins in which hypochlorous acid and an olefinic body are repeatedly supplied to an aqueous reaction medium `until the chlorhydrin has accumulated in solution to a substantial extent.

20. The process of making chlorhydrins, which consists in bringing an unsaturated hydrocarbon in gaseous state into contact' with a solution of hypochlorous acid, in the presence of a material capable of reacting with hydrochloric acid but not with hypochlorous acid, leading o-f the mixture'of solutions thus formed, regenerating hypochlorous acid in said mixture of solutions and subjecting said mixture to the action of an unsaturated hydrocarbon iny gaseous state.

21. The process of making chlorhydrins, wh ich consists in producing a mixed solution of hypochlorous acid and a salt of a weak acid, which will react With hydrochloric acid but not with hypochlorous acid contacting said solution with an unsaturated hydrocarbon in gaseous state, then ycontacting the resultant solution with chlorin to regenerate hypochlorous acid therein, treating the resultant mixed solution to form more chlorhydrin therein, and finally recovering the chlorhydrin therefrom. v

22. The process of making chlorhydrins, which consists in preparing a mixed solution of hypochlorous acidv and a salt ofa weak acid, which will react with hydrochloric acid but not with hypochlorous acid contacting an unsaturated hydrocarbon in gaseousl state with said mixed\ solution, whereby chlorhydrin and a soluble chloride are formed, and finally separating the chlorhydrinfrom the solution containing the soluble chloride.

23. The method of making chlorhydrin, which consists in bringing water in a closed circuit into contact with an opposed stream i first of chlorine gas, then of ethylene, and introducing at one point in the circuit a mild neutralizing agent adapted to react with hydrochloric acid, but not with hypochlo-` rous acid formed by the absorption of the aforesaid gases.

In testimony whereof, I affix my signature.

BYRON E. ELDRED. y 

